Manufacture of new coloring matters



Patented Sept. 10, 1946 MANUFACTURE OF NEW-"COLORING MATTERS I MauriceArthur- Thorold Rogers, Blackley, Manchester,-England, ,assignor toImperial Chemical Industries Limited, Britain a corporation of' Great.No Drawing. Application July 9, 12943, 'S eriaLNo. 494,120. In, GreatBritainJuly 13,1942

3 Claims.

The present invention-relates to the manufacture of new coloringmatters.

In British application No. 16,2'76/41, and in copendin'g" applicationSerial No. 457,2'28,*filed September 3, '1 942,,.:now' U. 1S. Patent2,382,914, there' are described tetraaryl aza-dipyrromethinesofxformula:

and in copending application No. 494,126, filed Ju1y 9, 1943, there aredescribed tetraaryldipyrromonomethines of formula I m '-g n, v-Q=G vi R'(IL--CR=CIZ l-R where R R It, and'R. stand for aryl radicals, forexample of-the benzene orinaphthalene series,

substituted or not, the same ordifferent, where R and R each. stand forhydrogen or for a non-reactive substituent, the same or difierent,

for example, an'aryl-,,,alkyl-, alkylamino-, benzylideneaminooracylaminoradical, and where R. stands for hydrogen or an alkyl-, aralkylor aryl-radical, or forra heterocyclic residue.

The present invention is directed to the production of metal complexes,from. these compounds that is to say, from :compounds of the formula NIf include 2:2 4 :4 -tetraphenyl-aza-dipyrrometh- 50 2 2 :2 :4 1 4tetraphenyl-meso -phenyl-dipyrromonomethine,

The metal complexes may be formed by using the metals themselves, forexample in a finely 5 divided form, or by "using salts, for example theacetates, sulphates, chlorides, phosphates or double salts such asdichromates. Good results have been obtained with, for example, copperacetate, copper sulphate, zinc acetate, chromimn fluoride, cobaltsulphate, cobaltacetate, and nickel acetate. V I r The reaction may becarried out by heating the reagents by' themselves or in'the' presenceof a solventfor one or both.

Alternatively, when metal complexes are to be made from water-solublederivatives of tetraaryl-aza dipyrromethines ortetraaryldipy-rromonomethines, for example, their sulphonic acidderivatives'which are described in 'copen'ding application Serial No.482,479, filed April '9', 1943, now U. S. Patent-2;382, 91-7, or thesalts of their amino-derivatives, they may be made by treating dyeingsof these Water-soluble compounds, for example on wool, with aqueoussolutions of the metal salts. In this way, the metal complexes areformed on the fibre.-

The invention is illustrated'but not limited by the following examples,in which the parts are expressed by Weight.

Example I,

1 part of 2: :4:4"-tetraphenyl-aza-dipyrromethine, 0.5 part of copperacetate and 50 parts of butanol:are'rboiledtogether for 1 hourrand thecoppery brown crystalline material which forms is collected byfiltration. The product analyses for C64H44N6Cu, and has the probablformula:

OH=CPh rh-c i-- in It is sparingly solubl in nitrobenzene, dioxan,pyridine and dimethylformamide forming solutions which are blue incolor. I In a similar manner, cobalt, nickel and zinc acetates yield thecorresponding complexes.

Example II In place of the aza methine in Example I there is used 1 partof 2:2":4:4-tetraphenyldipyrromonomethine. The copper complex formscop-. pery brown platelets, which are crystallised from a mixture ofpyridine and methyl alcohol in the form of platelets.

The product analyses for CcsHnsNeCu and is believed to have a structuresimilar to that assigned to the product of EXam-' ple I.

Example III p The disulphonic acid derivative of 2122414-tetraphenyl-aza-dipyrromethine is dyed on to wool from an acid dyebath.The dyed Wool so obtained is heated in a aqueous solution of coppersulphate for 1 hour at 80-90 C. The color of the dyeing changes from areddish-blue to a greener color as the copper complex is formed.

Example IV A compound of the formula T M03931 N(CHa)aI 4 where R R R andR stand for aryl radi cals, R and R" each are a member of the groupconsisting of hydrogen, arylalkyl-, alkylamino-, benzylideneamino-, andacylaminoradicals, A is a member of the group consisting of nitrogen andthe group l I wherein R is a member of the group consisting of hydrogen,alkyl-, aralkyl-, aryl-, and heterocyclic radicals; and B is a metal ofthe group consisting of 'copper zinc, nickel, cobalt, chromium, andcadmium.

2. Process for the manufacture of metal complexes which comprisesbringing into reaction with each other a, compound of the generalformula:

where R R RW, and R tand for aryl radicals, R and R each are a member.of the group consisting of hydrogen, ary1-, alkyl-, alkylamino-,

benzylideneamino-, and acylamino radicals, Aisa. member of the groupconsisting of nitrogen and the group 1 wherein'R is a member of thegroup consisting of hydrogen, alkyl-, aralkyl-, aryl-, and heterocyclicradicals, with a member taken from the group consisting of copper, zinc,nickel, cobalt, chromium, and cadmium and their salts.

3. The compound of the formula:

n o-P11 Ph-C=GH v Ph--C 0-N=o C-Ph 7 Cu ROGERS.

